CN106803570A - A kind of lithium battery SiCO carbon nano-tube coextruded film electrodes - Google Patents
A kind of lithium battery SiCO carbon nano-tube coextruded film electrodes Download PDFInfo
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Abstract
The invention discloses a kind of lithium battery SiCO carbon nano-tube coextruded film electrodes, it is characterised in that：Including monocrystalline silicon substrate（1）, monocrystalline silicon substrate（1）On be sequentially provided with TiN barrier layers（2）, Cu film layers（3）, CuO film layers（4）, SiCO film layers A（5）, Ni Catalytic Layers（6）, carbon nanotube layer（7）With SiCO film layers B（8）.The present invention not only can effectively improve the cyclical stability of electrode, and monofilm thickness can be substantially reduced, and larger thin film system thickness can be obtained again, so as to improve chemical property of the material in high power charging-discharging.
Description
Technical field
The present invention relates to a kind of field of lithium, particularly a kind of lithium battery SiCO- carbon nano-tube coextruded film electrodes.
Background technology
Lithium ion has the series of advantages such as energy high, long service life, lightweight, small volume because of it, causes international electricity
Chi Jie and the common concern and attention of scientific and technological circle.Lithium battery applications mainly include portable unit energy-storage battery and new-energy automobile
Use electrokinetic cell.The former mainly includes 3C Product, i.e. computer, communication and consumption electronic product.Global cellphone subscriber's quantity with
The speed of 15%-25% or so is increasing, and the battery of 50%-70% all uses the development of the notebook computer of lithium battery, will all make lithium
The demand of ion battery increases year by year.It is electronic as countries in the world are more paid attention to energy security and environmental protection in strategy
Automobile as the new industry of strategic type the characteristics of its energy-conservation, low emission to be greatly developed by various countries.Development new-energy automobile, be
The strategic demand for break away from the dependence to fossil energies such as oil, preserving the ecological environment and ensure national energy security.
Electrode is the core component of lithium ion battery, and electrode material be determine lithium battery integrated performance it is good and bad it is crucial because
Element, exploitation high performance electrode material of new generation is always the important directions of lithium battery research.At present in lithium ion battery negative material
Most widely used graphite theory gram volume is 372 mAhg in material-1, this reaches far away the various portable products of fast development
The especially high power capacity demand of new-energy automobile power battery；Additionally, graphite linings are easily gradually peeled off in charge and discharge process, from
And influence its cycle performance.Silicon has capacity very high（Theoretical value reaches about 4200 mAhg-1）, but silicon is in Lithium-ion embeding
Its volumetric expansion is very big afterwards, so as to its capacity can be caused constantly to reduce in charge and discharge cycles, current silica-base material is in circulation
Deficiency in performance limits its further practical application.The interlamellar spacing of CNT be more than graphite, this be more beneficial for lithium from
The diffusion of son, lithium ion can not only be embedded in tube core, can also be embedded in the gap between pipe, be conducive to further improving putting for lithium battery
Capacitance and current density.Carbon nanotube electrode is at present major problem is that irreversible capacity is big and circulation reliability is not enough.Most
Nearly research shows that the SiCO ceramics of high carbon content have spy in good chemical property and relatively low cost, especially SiCO
Some carbon web frames can enter row buffering and absorption to its Volume Changes in charge and discharge process, make material in charge and discharge process
It is middle to keep preferable reliability.But SiCO there is also the problem to be resolved such as charge and discharge electric hysteresis, make its cycle performance not yet
Reach the requirement of commercial applications.
The content of the invention
It is an object of the present invention to provide a kind of lithium battery SiCO- carbon nano-tube coextruded film electrodes.The present invention is not only
The cyclical stability of electrode can be effectively improved, and monofilm thickness can be substantially reduced, can obtain larger thin again
Film system thickness, so as to improve chemical property of the material in high power charging-discharging.
Technical scheme：A kind of lithium battery SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：Bag
Monocrystalline silicon substrate is included, TiN barrier layers, Cu film layers, CuO film layers, SiCO film layers A, Ni are sequentially provided with monocrystalline silicon substrate
Catalytic Layer, carbon nanotube layer and SiCO film layers B.
With in SiCO- carbon nano-tube coextruded film electrodes, the thickness on the TiN barrier layers is 95- to foregoing lithium battery
105nm。
With in SiCO- carbon nano-tube coextruded film electrodes, the thickness of the Cu film layers is 290-310 to foregoing lithium battery
The thickness of nm, CuO film layer is 95-105 nm.
With in SiCO- carbon nano-tube coextruded film electrodes, the thickness of the SiCO film layers A is 190- to foregoing lithium battery
210 nm；The thickness of the Ni Catalytic Layers is 45-55 nm；The thickness of the carbon nanotube layer is 95-105 nm；The SiCO
The thickness of film layer B is 190-210 nm.
With in SiCO- carbon nano-tube coextruded film electrodes, its preparation method is carried out foregoing lithium battery in the steps below：
1. monocrystalline silicon substrate is cleaned by ultrasonic 8 minutes with acetone, then cleans 8 points with deionized water and alcohol ultrasonic wave respectively
Clock；
2. three times steps are repeated 1., then is dried in vacuum drying chamber；
3. ion beam sputtering cleaning is carried out to monocrystalline silicon substrate under vacuum；
4. carbon nanotube layer is prepared using hot filament CVD, and remaining film layer is prepared with radio frequency sputtering method；Radio frequency splashes
The method of penetrating is, in the environment of the argon gas that purity is 99.99% is as working gas, using the method for magnetron sputtering by sputtering target material
It is splashed to monocrystalline silicon substrate surface and forms liner body；The sputtering target material be respectively TiN, Cu, CuO, Si and graphite, Ni, Si and
Graphite；The liner body is respectively that TiN barrier layers, Cu film layers, CuO film layers, SiCO film layers A, Ni Catalytic Layer and SiCO are thin
Film layer B.
Foregoing lithium battery is prepared with SiCO- carbon nano-tube coextruded film electrodes using hot filament CVD
Carbon nanotube layer.
With in SiCO- carbon nano-tube coextruded film electrodes, the sputtering target material is placed in away from monocrystalline silicon substrate foregoing lithium battery
The distance of plate is 6cm.
With in SiCO- carbon nano-tube coextruded film electrodes, the target TiN splashes foregoing lithium battery in sputter procedure
Pressure is penetrated for 0.6Pa, power is 200w, and sputtering time is 60min, and argon flow amount is 30sccm；The target Cu was being sputtered
Cheng Zhong, sputtering pressure is 0.8Pa, and power is 150w, and sputtering time is 120min, and argon flow amount is 40sccm；The target CuO
In sputter procedure, sputtering pressure is 0.8Pa, and power is 100w, and sputtering time is 60min, and argon flow amount is 40sccm；It is described
In sputter procedure, sputtering pressure is 0.3Pa for Si and graphite, and power is 300w, and sputtering time is 90min, and argon flow amount is
25sccm；In sputter procedure, sputtering pressure is 0.6Pa to the Ni, and power is 200w, and sputtering time is 100min, argon gas stream
It is 30sccm to measure.
With in SiCO- carbon nano-tube coextruded film electrodes, the SiCO film layers A is with nano junction to foregoing lithium battery
The SiCO film layers of structure；The SiCO film layers B is the SiCO film layers with loose structure.
Foregoing lithium battery with SiCO- carbon nano-tube coextruded film electrodes, the SiCO with nano structure
Film layer preparation method is carried out in the steps below：1. by the hydrofluoric acid solution 2 minutes of sample immersion concentration 30%；2. concentration is immersed
10% hydrofluoric acid solution 30 minutes；3. the hydrofluoric acid clean for using distilled water that specimen surface is remained is clean, and it is Celsius to be put into 100
Degree drying baker is dried 30 minutes removal residual moistures and is obtained final product.
Foregoing lithium battery with SiCO- carbon nano-tube coextruded film electrodes, the SiCO with porous nanometer structure
Film layer preparation method is carried out in the steps below：1. by the hydrofluoric acid solution 4 minutes of sample immersion concentration 50%, it is then immersed in dense
Spend 30% hydrofluoric acid solution 80 minutes；2. the hydrofluoric acid clean for using distilled water that specimen surface is remained is clean, and it is Celsius to be put into 150
Degree drying baker is dried 60 minutes removal residual moistures and is obtained final product.
Compared with prior art, the present invention is by by the electrode material phase of SiCO and CNT both great potentials
With reference to by specific capacity and the gradient design of mechanical property, comprehensively embodying the respective advantage of material and mutually cover the shortage, most
The novel thin film electrode system with excellent electrochemical characteristic and mechanical property is obtained eventually.Using magnetically controlled sputter method and silicon, aluminium,
The targets such as graphite prepare thin film system, have the advantages that good tack, low cost, composition be controllable and low temperature, and use chemistry heavy
Area method prepares CNT has the advantages that process simple and fast, without expensive instrument, be especially suitable for industrialization large-scale production.
Experimental results show that the membrane electrode system has excellent electrochemical properties and mechanical property：It circulates specific capacity first
Up to 2231mAhg-1, after 60 times circulate, specific capacity still has 1786 mAhg-1, capacitance loss is only 20%；Thin film system
Interface bond strength reaches 49N；Different matrix temperature prepare gained membrane electrode system Young's modulus 145-189GPa it
Between, hardness is between 9.2-11.4GPa.
Thin-film material has larger specific surface area, can suitably alleviate generation volume of the electrode material in discharge and recharge swollen
It is swollen, and control capability decay, therefore electrode material membraneization can effectively improve the cyclical stability of electrode.Additionally, film
Material can also effectively shorten lithium ion qian during embedded abjection and move path as electrode, and improve diffusion rate,
So as to improve chemical property of the material in high power charging-discharging.Using the method for multilayer film, monofilm thickness can be significantly
Reduce, and larger thin film system thickness can be obtained.
This membrane electrode system has SiCO and the respective chemical property of CNT and material property, and CNT is carried
For storage lithium specific capacity very high, SiCO also substantially increases the stability of CNT while high specific capacity is provided；
And CNT charge/discharge rates are fast, this significantly improves the sluggish problem of SiCO discharge and recharges.SiCO-Ni- CNTs-porous
SiCO systems have good swell gradient, it is ensured that each layer film can combine closely in charge and discharge process, it is to avoid deintercalation
Lithium causes the obscission that volumetric expansion is caused.And the preparation of SiCO surface nano-structures and loose structure can further optimize
The diffusion of lithium ion and the bond strength of thin film system.
Brief description of the drawings
Fig. 1 is structural representation of the invention；
Fig. 2 is the cycle characteristics figure of membrane electrode system；
Fig. 3 is the cut test sound emission figure of thin film system.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples, but be not intended as to the present invention limitation according to
According to.
Embodiment.A kind of lithium battery SiCO- carbon nano-tube coextruded film electrodes, are constituted as shown in figure 1, including monocrystalline silicon
Substrate 1, is sequentially provided with TiN barrier layers 2, Cu film layers 3, CuO film layers 4, SiCO film layers A5, Ni and urges on monocrystalline silicon substrate 1
Change layer 6, carbon nanotube layer 7 and SiCO film layers B8.
The thickness on the TiN barrier layers 1 is 95-105nm.
The thickness of the Cu film layers 2 is 95-105 nm for the thickness of 290-310 nm, CuO film layer 4.
The thickness of the SiCO film layers A5 is 190-210 nm；The thickness of the Ni Catalytic Layers 6 is 45-55 nm；It is described
The thickness of carbon nanotube layer 7 is 95-105 nm；The thickness of the SiCO film layers B8 is 190-210 nm.
Described lithium battery is carried out in the steps below with the preparation method of SiCO- carbon nano-tube coextruded film electrodes：
1. monocrystalline silicon substrate is cleaned by ultrasonic 8 minutes with acetone, then cleans 8 points with deionized water and alcohol ultrasonic wave respectively
Clock；
2. three times steps are repeated 1., then is dried in vacuum drying chamber；
3. ion beam sputtering cleaning is carried out to monocrystalline silicon substrate under vacuum；
4. in the environment of the argon gas that purity is 99.99% is as working gas, sputtering target material is splashed using the method for magnetron sputtering
It is mapped to monocrystalline silicon substrate surface and forms liner body；The sputtering target material is respectively TiN, Cu, CuO, Si and graphite, Ni, Si and stone
Ink；The liner body is respectively TiN barrier layers, Cu film layers, CuO film layers, SiCO film layers A, Ni Catalytic Layer and SiCO films
Layer B.Carbon nanotube layer can be prepared by a conventional method, and can prepare carbon nanotube layer using hot filament CVD.
The distance that the sputtering target material is placed in away from monocrystalline silicon substrate is 6cm.
In sputter procedure, sputtering pressure is 0.6Pa to the target TiN, and power is 200w, and sputtering time is 60min, argon
Throughput is 30sccm；In sputter procedure, sputtering pressure is 0.8Pa to the target Cu, and power is 150w, and sputtering time is
120min, argon flow amount is 40sccm；In sputter procedure, sputtering pressure is 0.8Pa to the target CuO, and power is 100w, is splashed
The time is penetrated for 60min, argon flow amount is 40sccm；In sputter procedure, sputtering pressure is 0.3Pa, power for the Si and graphite
It is 300w, sputtering time is 90min, and argon flow amount is 25sccm；In sputter procedure, sputtering pressure is 0.6Pa, work(to the Ni
Rate is 200w, and sputtering time is 100min, and argon flow amount is 30sccm.
The SiCO film layers A is the SiCO film layers with nanostructured；The SiCO film layers B is with porous knot
The SiCO film layers of structure.
The SiCO film layers preparation method with nano structure is carried out in the steps below：1. sample is immersed dense
The hydrofluoric acid solution of degree 30% 2 minutes；2. the hydrofluoric acid solution of concentration 10% is immersed 30 minutes；3. it is with distilled water that specimen surface is residual
The hydrofluoric acid clean stayed is clean, and is put into 100 degrees Celsius of drying bakers and dries 30 minutes removal residual moistures and obtain final product.
The SiCO film layers preparation method with porous nanometer structure is carried out in the steps below：1. sample is immersed dense
The hydrofluoric acid solution of degree 50% 4 minutes, is then immersed in 30% hydrofluoric acid solution of concentration 80 minutes；2. it is with distilled water that specimen surface is residual
The hydrofluoric acid clean stayed is clean, and is put into 150 degrees Celsius of drying bakers and dries 60 minutes removal residual moistures and obtain final product.
The present invention, can be as follows in specific preparation：
1st, thin film system preparation method
Carbon nanotube layer is prepared using hot filament CVD, other films are prepared with radio frequency sputtering method.Magnetron sputtering method
It is 99.99 % to use graphite, silicon, nickel, copper, cupric oxide and nitridation titanium target purity, is passed through argon gas and oxygen that purity is 99.99%
Respectively as working gas and reacting gas.Monocrystalline silicon substrate carries out prerinse first, first with acetone ultrasonic cleaning 8 minutes, so
Cleaned 8 minutes with deionized water and alcohol ultrasonic wave respectively afterwards, repeat said process and clean three times, finally in vacuum drying chamber
Drying.Before deposition film, also ion beam sputtering cleaning is carried out to substrate in high vacuum conditions, its primary effect is
Fall the foreign particle of substrate surface, thorough exposed real substrate surface atom；Ions Bombardment can make the atom of substrate surface live
Change, improve substrate surface atomic pola-rizability, adhesive strength of the enhanced film to substrate.Sputtering target material is placed in away from substrate distance 6
Cm, the main preparation parameter of each layer film is as shown in table 1.In hot filament CVD prepares CNT method, lamp
Silk uses the tantalum wire of a diameter of 0.5mm, and heating-up temperature is 2400 DEG C；Reacting gas is CH4And H2, wherein CH4Concentration be 5%,
Pressure is 1.5 × 103 Pa, sedimentation time is 8-10min.
The magnetron sputtering preparation parameter of each layer film of table 1.
2nd, the preparation method of SiCO film surfaces nanostructured and loose structure
The nanostructured of SiCO is mainly made up of three-dimensional carbon net, silica and transition zone, and carbon atom gathers together and forms net
Shape structure, and most of space in silica-filled network structure.Hydrofluoric acid can with the silicon dioxde reaction in SiCO but
Will not be reacted with carbon net, the silica of SiCO films can be removed, so as to obtain with surface nano-structure or many
The SiCO films of pore structure.
The method that SiCO film surface nanostructureds are prepared with chemical corrosion method：Sample is immersed into hydrofluoric acid solution first
（Concentration 30%）2 minutes, it is then immersed in low concentration hydrofluoric acid solution（10%）30 minutes.Specimen surface is remained with distilled water finally
Hydrofluoric acid clean it is clean, and be put into 100 degrees Celsius of drying bakers and dry 30 minutes removal residual moistures.
The method that SiCO film loose structures are prepared with chemical corrosion method：Film sample is immersed into hydrofluoric acid solution first
（Concentration 50%）5 minutes, it is then immersed in low concentration hydrofluoric acid solution（20%）60 minutes.Specimen surface is remained with distilled water finally
Hydrofluoric acid clean it is clean, and be put into 150 degrees Celsius of drying bakers and dry 90 minutes removal residual moistures.
3rd, the performance verification of membrane electrode system
Using high-purity lithium metal as to electrode, button cell is assembled into the glove box full of argon gas, its structure diagram is such as
Shown in lower.Electrolyte is the LiPF of 1mol/L by solute6, solvent is ethylene carbonate+dimethyl
carbonate + ethyl methyl carbonate （Mass ratio 1：1：1）Solution be formulated, barrier film be micropore poly- third
Alkene film Celgard-2300.In the pre-assembly, button cell shell is cleaned up with alcohol/acetone, and is dried 5 hours, to remove
Remove surface and oil contaminant and moisture.Then Si carbon-base ceramic electrical pole piece, battery case, barrier film, diaphragm seal for will preparing etc. send into gloves
Assembled in case, and electricity consumption immediately moves stamping machine by battery pressurization.At room temperature, it is 0.1mA to use charging and discharging currents density
cm-2, cyclic voltammetry scan speed is 0.5mVs-1, cyclic voltammetry is carried out in multi-channel electrochemical system, in LAND-
Constant current charge-discharge test is carried out on CT2001A battery test systems.
Fig. 2 is the change curve of the cycle performance curve of membrane electrode system, i.e. specific capacity with cycle-index.Can by figure
Know, membrane electrode system circulates specific capacity up to 2231mAhg first-1, as cycle-index increases, though specific capacity has slightly subtract
Small trend, but its reduction trend tends to flat after 40 circulations.After 60 times circulate, specific capacity still has 1786
mAhg-1, far above graphite cathode material conventional at present（372 mAhg-1）, and its capacitance loss is only after 60 times circulate
20%, the reversible capacity much smaller than CNT loses（>50%）.
The different matrix temperature that table 2 is obtained for nano-indenter test（Prepare SiCO）The Young's modulus of lower thin film system and hard
Degree, it can be seen that the Young's modulus of laboratory sample between 145-189GPa, hardness between 9.2-11.4GPa, thin film system
With excellent mechanical property.
The different matrix temperature of table 2.（Prepare SiCO）The Young's modulus and hardness of lower thin film system
Fig. 3 is the result of thin film system cut test.Cut test is generally applicable to material science and tribological field carrys out table
The ability of material resistance delineation and cutting is levied, while intuitively reflecting the bond strength between film and matrix material.Can be with
Find out, the interface bond strength of thin film system reaches 49N, embody good interfacial combined function, illustrate to thin film system
Structure design plays an important role.
Claims (10)
1. a kind of lithium battery SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：Including monocrystalline silicon substrate（1）, monocrystalline
Silicon substrate（1）On be sequentially provided with TiN barrier layers（2）, Cu film layers（3）, CuO film layers（4）, SiCO film layers A（5）, Ni urges
Change layer（6）, carbon nanotube layer（7）With SiCO film layers B（8）.
2. lithium battery according to claim 1 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：The TiN
Barrier layer（1）Thickness be 95-105nm.
3. lithium battery according to claim 1 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：The Cu
Film layer（2）Thickness be 290-310 nm, CuO film layers（4）Thickness be 95-105 nm.
4. lithium battery according to claim 1 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：It is described
SiCO film layers A（5）Thickness be 190-210 nm；The Ni Catalytic Layers（6）Thickness be 45-55 nm；The CNT
Layer（7）Thickness be 95-105 nm；The SiCO film layers B（8）Thickness be 190-210 nm.
5. SiCO- carbon nano-tube coextruded film electrodes of the lithium battery according to claim 1,2,3 or 4, it is characterised in that：
Its preparation method is carried out in the steps below：
1. monocrystalline silicon substrate is cleaned by ultrasonic 8 minutes with acetone, then cleans 8 points with deionized water and alcohol ultrasonic wave respectively
Clock；
2. three times steps are repeated 1., then is dried in vacuum drying chamber；
3. ion beam sputtering cleaning is carried out to monocrystalline silicon substrate under vacuum；
4. carbon nanotube layer is prepared using hot filament CVD, and remaining film layer is prepared with radio frequency sputtering method；Radio frequency splashes
The method of penetrating is, in the environment of the argon gas that purity is 99.99% is as working gas, using the method for magnetron sputtering by sputtering target material
It is splashed to monocrystalline silicon substrate surface and forms liner body；The sputtering target material be respectively TiN, Cu, CuO, Si and graphite, Ni, Si and
Graphite；The liner body is respectively that TiN barrier layers, Cu film layers, CuO film layers, SiCO film layers A, Ni Catalytic Layer and SiCO are thin
Film layer B.
6. lithium battery according to claim 5 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：It is described to splash
The distance that material of shooting at the target is placed in away from monocrystalline silicon substrate is 6cm.
7. lithium battery according to claim 5 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：The target
In sputter procedure, sputtering pressure is 0.6Pa to material TiN, and power is 200w, and sputtering time is 60min, and argon flow amount is
30sccm；In sputter procedure, sputtering pressure is 0.8Pa to the target Cu, and power is 150w, and sputtering time is 120min, argon
Throughput is 40sccm；In sputter procedure, sputtering pressure is 0.8Pa to the target CuO, and power is 100w, and sputtering time is
60min, argon flow amount is 40sccm；In sputter procedure, sputtering pressure is 0.3Pa for the Si and graphite, and power is 300w, is splashed
The time is penetrated for 90min, argon flow amount is 25sccm；In sputter procedure, sputtering pressure is 0.6Pa to the Ni, and power is 200w,
Sputtering time is 100min, and argon flow amount is 30sccm.
8. lithium battery SiCO- carbon nano-tube coextruded film electrodes according to claim 1 or 5, it is characterised in that：It is described
SiCO film layers A is the SiCO film layers with nanostructured；The SiCO film layers B is the SiCO films with loose structure
Layer.
9. lithium battery according to claim 8 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：The tool
The SiCO film layers preparation method for having nano structure is carried out in the steps below：1. sample is immersed the hydrofluoric acid of concentration 30%
Solution 2 minutes；2. the hydrofluoric acid solution of concentration 10% is immersed 30 minutes；3. use the hydrofluoric acid that distilled water remains specimen surface clear
Wash clean, and be put into 100 degrees Celsius of drying bakers and dry 30 minutes removal residual moistures and obtain final product.
10. lithium battery according to claim 8 SiCO- carbon nano-tube coextruded film electrodes, it is characterised in that：The tool
The SiCO film layers preparation method for having porous nanometer structure is carried out in the steps below：1. sample is immersed the hydrofluoric acid of concentration 50%
Solution 4 minutes, is then immersed in 30% hydrofluoric acid solution of concentration 80 minutes；2. use the hydrofluoric acid that distilled water remains specimen surface clear
Wash clean, and be put into 150 degrees Celsius of drying bakers and dry 60 minutes removal residual moistures and obtain final product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108520974A (en) * | 2018-06-11 | 2018-09-11 | 四会市恒星智能科技有限公司 | A kind of lithium ion battery and preparation method thereof |
| CN108807901A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | The compound negative material of lithium ion battery |
| CN108807898A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN112881475A (en) * | 2021-01-08 | 2021-06-01 | 温州大学 | Porous SiCO-MoO3 high-temperature hydrogen sensor and preparation method thereof |
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| CN103022434A (en) * | 2012-11-23 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Precursor ceramic-carbon nano tube composite material and preparation method thereof |
| CN104993115A (en) * | 2015-08-03 | 2015-10-21 | 温州大学 | Lithium battery SiCO-Si gradient thin film electrode system and preparing method thereof |
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| CN103022434A (en) * | 2012-11-23 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Precursor ceramic-carbon nano tube composite material and preparation method thereof |
| CN104993115A (en) * | 2015-08-03 | 2015-10-21 | 温州大学 | Lithium battery SiCO-Si gradient thin film electrode system and preparing method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520974A (en) * | 2018-06-11 | 2018-09-11 | 四会市恒星智能科技有限公司 | A kind of lithium ion battery and preparation method thereof |
| CN108807901A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | The compound negative material of lithium ion battery |
| CN108807898A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN108807901B (en) * | 2018-06-11 | 2020-12-11 | 钟旭航 | Composite negative electrode material for lithium ion battery |
| CN108807898B (en) * | 2018-06-11 | 2021-02-05 | 信丰永冠塑电科技有限公司 | Preparation method of lithium ion battery negative electrode material |
| CN112881475A (en) * | 2021-01-08 | 2021-06-01 | 温州大学 | Porous SiCO-MoO3 high-temperature hydrogen sensor and preparation method thereof |
| CN112881475B (en) * | 2021-01-08 | 2023-04-07 | 温州大学 | Porous SiCO-MoO3 high-temperature hydrogen sensor and preparation method thereof |
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